Hydrocarbon tolerant hair fixing compositions

ABSTRACT

This invention presents two series of novel hair fixing compositions, the first comprising copolymers of acrylates, N-substituted acrylamides and acrylic acid; and the second comprising copolymers of vinyl acetate or propionate, vinyl esters of α-branched carboxylic acids, and alkyl maleates. Such materials, when neutralized with NaOH, KOH, or mixtures of these bases with certain long chain amines, exhibit an enhanced tolerance of non-halogenated hydrocarbons and are particularly useful.

This application is a division of application Ser. No. 166,332 filedMar. 10, 1989.

BACKGROUND OF THE INVENTION

This invention relates to novel hair fixing compositions which exhibitsuperior hydrocarbon tolerance and are suitable for use in aerosolapplications wherein hydrocarbon propellants are used.

In order to be effective in aerosol hair spray formulations, the filmforming, polymeric binders utilized therein as well as the films derivedtherefrom must meet a rigid set of requirements. The binders used insuch formulations should be soluble in organic solvents; yet the filmscast from such hair spray formulations should, ordinarily, be eitherwater soluble or water dispersible in order to facilitate their easyremoval from the user's hair. As is readily visualized, this is anunusual combination of properties which is further complicated by therequirement that the binder used in such formulations be completelycompatible with the propellants and solvents ordinarily employedtherein. Further, the binders should be stable in the presence of, andunreactive with, the perfumes or other optional ingredients utilized inhair spray formulations.

In addition, the films cast from either aqueous or organic solventsolutions of these binders should be flexible and yet they should havesufficient strength and elasticity; they should adhere well to hair soas to avoid dusting or flaking off when the hair is subjected to varyingstresses; they should readily allow the hair to be recombed; they shouldmaintain a nontacky state despite varying environmental conditions; theyshould be clear, transparent and glossy and should maintain this clarityon aging; they should possess good anti-static properties; and, theyshould be easily removable by the use of water and/or soap or shampoo.

Many polymeric systems have been utilized in an attempt to meet thesestringent requirements. Among these are included; polyvinylpyrrolidone,copolymers of N-vinyl pyrrolidone with vinylacetate, 5-5'-dimethylhydantoinformaldehyde resins and copolymers of methyl vinyl ethers andmaleic acid half esters, etc. Though each of the latter systems has metat least some o the above cited requirements, none has exhibited all ofthese requirements to an optimum degree.

For example, carboxylated vinyl polymeric hair spray resins,particularly the carboxylated acrylate, and/or acetate based resins,have long been favored for use in aerosol hair spray formulations. Alsouseful are a class of carboxylated ester polymers comprising anacrylamide, an acidic film forming comonomer, and at least onepolymerizable comonomer which are described in U.S. Pat. No. 3,927,199.In order to obtain optimum benefits for the use of such acidic resins,it has been required to neutralize at least a portion, and preferablyall, of the available carboxyl functionalities with specific alkalinereagents, e.g. amines and aminohydroxy compounds, as described in, forexample, U.S. Pat. Nos. 2,996,471; 3,405,084; 3,577,517, etc. Thus,alkaline reagents which are suggested for such neutralizations includeammonia, lithium hydroxide, potassium hydroxide, sodium hydroxide,mono-, di- or tri-ethanolamine, mono-, di or tripropanolamine,morpholine, amino ethyl ethanol amine, amino metyl propanol, aminomethyl propanediol, hydroxy ethyl morpholine, and mixtures thereof. Thepurpose of this neutralization step is both to improve the watersolubility or dispersibility of the resin thus permitting easy removalfrom the hair by merely washing with shampoo and also to affect thedegree of flexibility of the resultant film when sprayed on the hair(i.e. to produce a soft film, normal film or a film suitable for "hardto hold" hair). Additionally, U.S. Pat. No. 4,192,861 teaches the use oflong chain amines for the neutralization of specific polymers in aerosolhairspray systems.

Recent ecological considerations have resulted in a shift away from theuse of certain halogenated propellants and cosolvents and toward the useof hydrocarbons as propellants in aerosol hair spray formulations. Insuch systems, the binder and any optional ingredients are dissolved in asuitable solvent, such as an alcohol, and the hydrocarbon serves as thepropellant. Unfortunately, the use of these propellants produces anumber of problems, some of which are due to the decrease in solubilityof the binder in the alcohol as the hydrocarbon content is increased toa level acceptable for use as a propellant. Thus, while the carboxylatedresin are soluble in the anhydrous alcohol-halocarbon systems of theprior art, and are the commercially preferred resins for their hairholding properties, their reduced solubility in the alcohol-hydrocarbonpropellant may render them unacceptable to the industry for use inaerosol systems containing high levels of hydrocarbon propellants.

Thus, there exists a need for hairspray formulations which exhibitdesirable hair fixing properties as well as high tolerance ofhydrocarbon propellants which are becoming increasingly important in theindustry.

SUMMARY OF THE INVENTION

It is an object of this invention to present a series of compositionssuitable for use as hair fixing compositions. It is further an object ofthis invention to present hair fixing compositions which exhibit a hightolerance for hydrocarbon propellants, such that they can be used inaerosol compositions using these propellants.

This invention presents novel hair fixing compositions which comprise aclass of copolymers of acrylates, N-substituted acrylamides, and acrylicacid; and a class of copolymers of vinyl acetate or propionate, vinylesters of α-branched carboxylic acids and alkyl maleates. Whenneutralized with neutralizing agents containing NaOH, KOH, or mixturesof NaOH and/or KOH with long chain amines such as those described inU.S. Pat. No. 4,192,861, these compositions have been found, quitesuprisingly, to exhibit superior tolerance to hydrocarbon propellantsused in aerosol hairsprays. This tolerance is especially noticeable atthe high levels of neutralization necessary for water removability.

Additionally, the compositions exhibit desirable hair-fixing propertiesand exhibit a clear, glossy, and durable film when applied to hair.

Since neutralization of the acidic polymers is required for goodremovability upon shampooing, the copolymers will generally beneutralized prior to incorporation in the hairspray formulation. Thisneutralization confers a dual benefit on the compositions, increasingnot only their shampoo removability but, unexpectedly, their toleranceof high levels of hydrocarbon propellant in the aerosol formulations.This permits a much higher polymer level to be realized in the hairsprayformulation and, consequently, a much drier spray. The fact that NaOHand KOH have this effect is suprising in view of the fact that thesecompounds themselves are not soluble in the non-polar hydrocarbons usedas propellants.

DETAILED DESCRIPTION OF INVENTION

3.1 Polymers Used In The Hairspray Formulations

3.1.1 Acrylate-Based Copolymers

One class of copolymers especially suited for use in hairsprayformulations containing hydrocarbon propellants are copolymerscontaining 40-60% (by wt.) of a C₃ -C₁₂, preferably C₃ -C₈, alkylmethacrylate, 20-40% (by wt) of a C₄ -C₁₀ N-substituted alkylacrylamide, and 10-25%, preferably 19-25% (by wt.) acrylic acid ormethacrylic acid, wherein the percentages total 100%. More preferably,these copolymers comprise 45-55% isobutylmethacrylate, 25-35% N t-octylacrylamide, and 19-25% acrylic acid. In a preferred embodiment of thisinvention, the composition is a copolymer comprising 51%isobutylmethacrylate, 30% N t-octyl acrylamide, and 19% acrylic acid.This polymer is a solid formulation which is soluble in alcohols andother materials which can be used as solvents used in hairsprayformulations such as methanol, ethanol, isopropanol, and acetone as wellas some other esters and ketones.

These copolymers exhibit superior hair-holding properties and, whenapplied as an aerosol to the hair, produce a hard, but flexible filmwhich displays excellent subjective properties such as high gloss, goodstatic resistance, and superior adhesion to hair.

These copolymers are insoluble in water, but become soluble whenneutralized as described in Section 3.2. This neutralization alsoconfers the distinct benefit of increasing their tolerance to thehydrocarbon propellant, permitting high levels of propellants, often60-80% or more of the formulation, to be present.

3.1.2 Vinyl-Based Copolymers

In addition to acrylate-based copolymers described above, the class ofcopolymers of vinyl acetate or vinyl propionate, vinyl esters of C₅ -C₁₈α-branched carboxylic acids, and monoalkyl maleates exhibit similarproperties in terms of hair holding properties and hydrocarbontolerance. This tolerance is also increased when the copolymer isneutralized.

Typical formulations of these copolymers comprise 20-35% (by wt.) ofvinyl acetate or vinyl propionate, 35-50% (by wt.) of a vinyl ester ofan α-branched carboxylic acid, and 25-40% (by wt.) of a C₃ -C₈ monoalkylmaleate, wherein the percentages total 100%. More preferably, thesecopolymers comprise 25-30% of vinyl acetate; 35-40% (by wt), vinylneodecanoate; and 35-40% (by wt), of a monoisobutyl maleate.

In a preferred embodiment of this invention, the copolymer comprises 25%vinyl acetate, 35% vinyl neo-decanoate, and 40% monoisobutyl maleate.

3.1.3 Optional Comonomers

In addition to the copolymers described in 3.1.1 and 3.1.2, theformulations can also contain from 5 to 20% of an optional comonomers.These monomers can be included to tailor and/or enhance certainproperties of the copolymer such as hair adherance, hardnees,flexibility, antistatic properties and the like. Among these comonomersare acrylic and methacrylic esters of aliphatic alcohols having from1-12 carbon atoms such as methyl, ethyl, propyl, butyl, octyl and laurylalcohol,; hydroxyalkyl esters of acrylic and methacrylic acids such ashydroxypropyl acrylate and methacrylate, hydroxybutyl acrylate andmethacrylate, hydroxystearyl acrylate and methacrylate and hydroxyethylacrylate and methacrylate; alkyl (C₁ -C₄) and amino alkyl (C₂ -C₄)esters of acrylic and methacrylic acids such as N,N-diethylaminoethylacrylate, N-t-butylaminopropyl acrylate, N,N-dimethylaminoethylmethacrylate, N-t-butylaminoethyl methacrylate, and the quaternizationproduct of dimethylaminoethyl methacrylate and dimethyl sulfate, diethylsulfate and the like; diacetone acrylamide; and vinyl esters such asvinyl acetate and vinyl propionate; styrene and alkyl-substitutedmonomers such as styrene and alpha-methyl styrene; C₁ -C₈ dialkylmaleates; N-vinyl pyrrolidone; and N-substituted alkyl (C₁ -C₈) maleamicacids.

3.2 Neutralization

As stated supra, water solubility of acidic polymer compositions used inhairsprays is achieved by neutralization with the appropriate alkalinematerial, such as NaOH or KOH. An unexpected benefit of neutralizationwith these materials, however, is that the hydrocarbon tolerance of thecopolymers of this invention is greatly increased, permitting highlevels of hydrocarbon propellant to be present in the resultanthairspray formulation. Further, since these agents are soluble inalcohol, the polymer compositions can be neutralized directly in thehair spray formulation, eliminating the need for an additionalpropearation step.

While many alkaline neutralizing agents may be employed to achieve waterremovability and some degree of hydrocarbon tolerance, maximalhydrocarbon tolerance is achieved by neutralization with NaOH, KOH, andmixtures of NaOH and/or KOH with long chain amines such as thosedescribed in U.S. Pat. No. 4,192,861 issued Mar. 11, 1980, to Micchelliet al., and incorporated herein by reference. However, the effect willbe observed with any neutralizing agent mixture so long as it containsNaOH and/or KOH as the predominant component.

For the purposes of the invention, the neutralization is preferably ascomplete as practical. Generally, at least 70%, preferably 80%, and morepreferably 90% or more of the carboxyl groups must be neutralized torealize a high degree of hydrocarbon tolerance. While total (100%)neutralization is possible, care must be taken to avoidover-neutralizing the system as the presence of excess neutralizingagents can effect formulatio stability.

3.3 Hairspray Formulations

In addition to the polymers which are neutralized by the appropriateneutralizing agent as described in Section 3.2, the only other essentialingredients in hairspray formulations are the solvent and thepropellant. While in some cases, particularly with chlorofluorocarbons,the propellant can be used as the solvent also, it is anticipated thatthe materials of this invention will be preimarily used withnon-halogenated solvents and hydrocarbon propellants (which cannot beused as solvents). In these formulations, the solvents of choice arealcohols, particularly the low boiling, more volatile alcohols.

In general, C₁ -C₄ straight and branched-chain alcohols can be used,with ethanol, propanol, and isopropanol being the preferred solvents. Inaddition to their excellent solubilizing properties, these solvents arequite volatile (and, thus, evaporate quickly) and are compatible withcontainers ordinarily used for pressurized aerosols.

While the polymers used in these formulations are compatable withvirtually any of the aerosol propellants known to those skilled in theart including halocarbons such as trichlorofluoromethane, it ispreferred to use non-halogenated hydrocarbons as the propellants toavoid the release of halocarbons into the atmosphere. Preferredpropellants are the lower boiling hydrocarbons, preferably C₃ -C₆straight and -branched chain hydrocarbons, more preferably propane,butane, isobutane and mixtures thereof. Other propellants suitable foruse in these formulations include ethers such as dimethyl ether.

In general, the method for preparing the hair spray formulations of thisinvention involves dissolving or diluting the copolymer in the selectedsolvent(s), adding the neutralizing agent, and subsequently adding anyoptional compounds whose presence may be desired, and combining theresultant solution with the selected aerosol propellant.

It should be noted that the novel hair spray formulations of thisinvention will, in all cases, contain at least four essentialcomponents. The first and second of these components are the activeingredients which comprise one or more of the above-describedcopolymers, which serve as the fixative for the formulation, and anappropriate neutralizing agent as described in Section 3.2. The thirdcomponent comprises one or more solvents which serve as vehicles for thebinder. The last component is the propellant which serves to effect thedischarge of the aforedescribed fixative and vehicle from the containerwherein the formulation is packaged. Water is not ordinarily present,but may be included in some formulations, as may other optionalingredients.

With regard to proportions, the final hair spray formulations typicallycontain the neutralized polymeric fixative in a concentration rangingfrom about 0.5 to 12%, by weight; the solvent in a concentration rangingfrom about 8 to 90%, by weight; and, the propellant concentrationranging from 10 to 85%, by weight, wherein all percentages total 100%.These proportions should, however, be considered as being merelyillustrative inasmuch as it may well be desirable to prepare operableformulations having concentrations of components which fall outside theabove suggested ranges for particular applications.

As stated supra, optional additives may also be incorporated into thehair fixing formulations of this invention in order to modify certainproperties thereof. Among these additives may be included; plasticizerssuch as glycols, phthalate esters and glycerin; silicones; emollients,lubricants and penetrants such as lanolin compounds, proteinhydrolyzates and other protein derivatives, ethylene oxide adducts, andpolyoxyethylene cholestrol; U.v. absorbers; dyes and other colorants;and, perfumes. As previously stated, the polymeric binders of thisinvention show little or no tendency to chemically interact with suchadditives.

The resulting hair fixing formulations exhibit all of thecharacteristics required of such a product. Their films are transparent,glossy, flexible and strong. They possess good antistatic properties,adhere well to hair, are easily removed by soapy water or shampoos,allow the hair to be readily recombed, do not yellow on aging, do notbecome tacky when exposed to high humidities, and have excellent curlretention under high humidity conditions.

4. Examples

The following examples further illustrate the preferred embodiments ofthis invention and are not intended to illustrate all embodiments.

4.1 Preparation of Copolymers

In a typical method for the polymerization of acrylate-based copolymersused in the aerosol hair fixing formulations of this invention, areaction vessel equipped with a condenser and a means for mechanicalagitation was charged with 51 parts (by wt.) isobutylmethacrylate, 30parts (by wt.) N t-octyl acrylamide, 19 parts (by wt.) acrylic acid, 2.0part (by wt.) benzoyl peroxide, and 100 parts (by wt.) of ethanol. Thecontents were heated to the reflux temperature of the system and heldthere for a period of 6 hours whereupon an additional 1.0 parts ofbenzoyl peroxide was added thereto. The system was then held at refluxfor an additional 4 hours whereafter the reacton was cooled to 30° C.and the polymer was recovered by standard separation means. This wasretained as Sample No. 2.

In a similar preparation, a vinyl-based copolymer was prepared bypolymerizing 25 parts (by wt.) vinyl acetate, 35 parts (by wt.) vinylneo-decanoate, and 40 parts (by wt.) mono-isobutylmaleate as describedabove. This was retained as Sample 3.

The other polymers evaluated in the subsequent examples were obtainedfrom commercial sources.

4.2 Preparation of Aerosol Formulations

In a typical preparation, the hairspray formulations were prepared asfollows:

1. The solvent was charged to an agitated mixing vessel at 15°-20° C.;

2. The polymer mixture is then added slowly to assure an evendispersion, and then neutralized to the desired % neutralization by theaddition of the neutralizing agent;

3. The mixture is stirred until the neutralized polymer is dissolved andany optional ingredients are then added;

4. The resultant solution is then filtered through a 5-10 microncartridge filter and subsequently charged, with the appropriate amountof propellant, to an aerosol container on an aerosol charging apparatus.

In this way, a wide variety of aerosol formulations were prepared as setforth in Table I.

                                      TABLE I                                     __________________________________________________________________________    Summary of Polymer Systems Used                                               to Prepare Hairspray Formulations                                                          Sample No.                                                       Monomer      1.sup.a                                                                         2.sup.b                                                                         3.sup.c                                                                         4 5 6 7 8.sup.i                                                                         9A.sup.f                                                                         9B.sup.g                                                                         10.sup.d                                                                         11.sup.e                                                                         12.sup.h                                                                         13                                __________________________________________________________________________    vinyl acetate    x x x x x   x  x           x                                 crotonic acid      x x                                                        vinyl neodecanoate                                                                             x x x                                                        t-octylacrylamide                                                                          x x       x x                  x                                 isobutylmethacrylate                                                                         x                                                              methyl methacrylate                                                                        x         x x                                                    hydroxypropyl                                                                 methacrylate x         x                                                      acrylic acid x x       x x         x                                          t-butylaminoethyl                                                             methacrylate x         x                                                      butyl acrylate         x                                                      t-butylacrylamide                  x                                          ethyl acrylate                     x                                          potassium acrylate                 x                                          methyl vinyl ether                    x                                       monobutyl maleate                     x                                       N--vinyl pyrollidone       x x  x        x                                    vinyl caprolactam                        x                                    dimethylaminoethyl                                                            methacrylate (DMAEMA)                    x                                    monoisobutyl malleate                                                                          x                          x                                 __________________________________________________________________________     .sup.a National Starch and Chemical Amphomer                                  .sup.b an acrylatebased copolymer of this invention, as prepared in           Example 4.1                                                                   .sup.c a vinylbased copolymer of this invention, as prepared in Example       4.1                                                                           .sup.d BASF "Ultra Hold 8"-                                                   .sup.e GAF Gantrez ES 425                                                     .sup.f PVP/VA 70/30 (by weight)                                               .sup.g PVP/VA 30/70 (by weight)                                               .sup.h GAF Gaffix VC713                                                       .sup.i PVP K30                                                           

These polymer samples were used in the subsequent examples using thestated solvent and neutralizing agents, and a hydrocarbon propellantcomprising approximately 80% (by wt.) isobutane and 20% (by wt.) propaneand designated A-46.

4.3 Hydrocarbon Tolerance

To assess the maximum quantity of hydrocarbon which can be tolerated inan aerosol formulation by the neutralized polymer mixtures, the polymersamples were formulated as 2% (by weight) solids using anhydrous ethanolas the solvent and A-46 propellant. The desired degree of neutralizationwas achieved using the stated neutralizing agent. The propellant wasthen added to the desired proportion and the formulations, in clearglass tubes, were chilled to -10° C. The maximum amount of propellanttolerated (i.e. that above which phase separation, as evidenced by theonset of turbidity, occurred) at this temperature was observed. Theresults were as follows:

                  TABLE II                                                        ______________________________________                                        Results of Hydrocarbon Tolerance Tests                                                       Max. Weight % A-46 Tolerated                                                  Neut. Agent                                                    Polymer                             KOH/OA.sup.c                              Sample No.                                                                            % Neutralization                                                                           AMP.sup.b                                                                             KOH    (75/25 molar)                             ______________________________________                                        1       90           35-40   <35    30-35                                     2       90           60      70     80                                        3       90           55      70     75                                        10.sup.a                                                                              100          65      65     75                                        4       90           25      --     --                                        5       90           30-35   <30    20-25                                     6       90           40-45   30-35  20-25                                     7       90           30-40   <10    10-25                                     11      8            30-35   <25    55-60                                     13      90           <35     35     --                                        ______________________________________                                         .sup.a This sample exhibited a 60-70% tolerance without neutralization        .sup.b 2-amino-2-methyl-1-propanol                                            .sup.c oleyl amine, a long chain amine                                   

The above data clearly demonstrate that neutralized acrylate-based(sample 2) and vinyl-based (sample 3) copolymers have exceptionally hightolerances of the hydrocarbon propellant when neutralized by KOH and KOHwith a long chain amine. By comparison, similar formulations such assample 1 and 16 and others did not exhibit this enhanced tolerance whenneutralized in the same manner. This is indicative of the superiorunexpected behavior of the neutralized copolymers of the instantinvention.

By way of comparison, non-ionic (non-carboxylated) polymers exhibit thefollowing tolerances under the same conditions:

                  TABLE III                                                       ______________________________________                                        Hydrocarbon Tolerances of Non-Ionic Polymer Formulations                      Polymer       Max. Weight %                                                   Sample No.    A-46 Tolerated                                                  ______________________________________                                        8             60-65                                                           9A            55                                                              9B            <50                                                             12            65                                                              ______________________________________                                    

Thus, it is seen that the hydrocarbon tolerance of neutralized samples 2and 3 is superior even to that of non-ionic polymers.

4.4. Effect of Varying Solvent

To assess the effect of changing the solvent, a series of experimentsidentical to those in 4.3 were conducted using isopropanol as thesolvent. The results are presented in Table IV.

                  TABLE IV                                                        ______________________________________                                        Results of Isopropanol Tests                                                                 Max. Weight % A-46 Tolerated                                                  Neut. Agent                                                    Polymer                             KOH/OA                                    Sample No.                                                                            % Neutralization                                                                           AMP     KOH    (75/25)                                   ______________________________________                                        2       90           60      70-75  80                                        3       90           55      70     70                                        13      90           <35     --     --                                        10      undet.       (as received, 70)                                        ______________________________________                                    

Once again, samples 2 and 3 exhibited high hydrocarbon tolerances.Sample 10, a commercial hydrocarbon tolerant formulation, exhibited amaximum tolerance of 70. Thus, these formulations of this inventioncompare favorably with formulation 10 and, inn fact, the KOH and KOH/OAneutralized (acrylate-based) formulation (sample 2) is superior to it.

4.5 Effect of Varying Neutralizing Agent

To assess the effect of changing the neutralizing agent, a series ofexperiments were run on Samples 2 and 3, using hydroxides of Group IAelements (alkali metals) in aqueous solution. In each experiment, aformulation containing 2% of neutralized polynmer (90% neutralization),28% anhydrous ethanol, and 70% A-46 propellant was prepared.Neutralization was performed using the indicated base. The mixture weresealed in glass tubes and gradually chilled until phase separation (asevidenced by the development of turbidity) develops; this temperature istermed the cloud point. The results are presented in Table V.

                  TABLE V                                                         ______________________________________                                        Results of Cloud Point Determinations                                         Polymer    Cloud Point (°C.)                                           Sample No. LiOH     NaOH      KOH   RbOH                                      ______________________________________                                        2          >20° C.                                                                         -30       -32   >20° C.                            3          >20° C.                                                                         -19       -14   >20° C.                            ______________________________________                                    

The results demonstrate that, even at high hydrocarbon contents, thesamples exhibit low, desirable cloud points when KOH and NaOH are usedas neutralizing agents, LiOH and RbOH, (which is insoluble in ethanol)do not appear to be good neutralizing agents.

4.6 Effect of Varying Propellants

To assess the effects of varying the propellant used in the formulation,samples 2 and 3, neutralized 90% with KOH, were subjected to the Example4.3 test to assess the maximum tolerance of dimethyl ether propellant at-10° C. Both samples showed a tolerance in excess of 80%, indicatingthat they are tolerant of ethers as well as hydrocarbons.

4.7 Subjective Evaluation of Hairspray Formulation

To assess the performance of various formulations samples were preparedand examined for hairspray properties using the following protocol.

1. In a blind study eight clean, dry, 10" sandwiches of brown hair arevertically suspended from the bound end.

2. Each front and back is sprayed with the test aerosol for 2 secondsfrom a distance of 6 inches.

3. A second set of eight swatches is sprayed with the control aerosol inthe same manner.

4. Each set is dried 30 minutes at room temperature.

5. The swatches are arranged in pairs consisting of one swatch from eachset.

6. Each member of an 8-member panel evaluates the pairs of treated hairswatches is then examined for the following properties:

(a) Stiffness: Swatches are handled by the panel member and rated in ascale of 1 (soft) to 5 (very stiff).

(b) Dry Combing: The swatches from the stiffness test are run betweenthe thumb and index finger twice to partially break the "crust". Eachswatch is combed gently several times and evaluated as to ease ofcombout on a scale of 1 to 5. The following rating definitions apply:

1-no to slight resistance to combing

2-moderate resistance

3-moderate to severe resistance

4-severe resistance to combing; snarling

5-complete resistance to combing.

(c) Adhesion of Hairspray Film to Hair: after the combing test both thehair swatches and the comb are visually inspected for flakeaccumulation. Swatches are rated on a scale of 1 (no flake appearing) to5 (severe flake).

(d) Gloss: Swatches from the flaking (adhesion) test are visuallyinspected and rated for gloss. A scale of 1 (excellent or high gloss) to4 (poor) is used.

(e) Static: Swatches from the gloss test are vigorously combed and ratedfor the extent of static flyaway generated A scale of 1 (excellent-nostatic flyaway) to 4 (poor-significant flyaway) is used.

The ratings of the 8 panelists in each determination are averaged andthe average is reported. Samples 2, 10, 3 and 4, neutralized to 90% withKOH, were examined in this test series. The results are summarized inTable VI.

                  TABLE VI                                                        ______________________________________                                        Results of Subjective Evaluation Tests                                        Polymer          Dry                                                          Sample No.                                                                            Stiffness                                                                              Combing  Adhesion                                                                             Gloss Anti-Static                            ______________________________________                                        2       2.25     2.50     1.50   1.50  2.00                                   10      2.00     1.75     1.75   1.50  2.00                                   3       2.25     2.50     1.00   1.75  1.50                                   4       2.00     1.75     2.00   1.75  1.00                                   ______________________________________                                    

It can be seen that the KOH neutralized polymers 2 and 3 not onlyprovide increased hydrocarbon tolerance, but also excellent hair sprayformulations which have equivalent or better performance characteristicsthan conventionally used hair spray polymers.

In is apparent that many modifications and variations of this inventionas hereinabove set forth may be made without departing from the spiritand scope thereof. The specific embodiments described are given by wayof example only and the invention is limited only by the terms of theappended claims.

What is claimed is:
 1. An improved hair fixing composition havingincreased hydrocarbon tolerance, for use in aerosol formulations,comprising a 40-60% (by wt.) of a tetrapolymer of the following monomerunits (1) C₃ -C₁₁ alkyl methacrylate, (2) 20-40% (by wt.) of a C₄ -C₁₀N-substituted alkyl acrylamide, (3) 10-25% (by wt.) of acrylic acid ormethacrylic acid, and (4) up to 20% (by wt.) of a comonomer selectedfrom the group consisting of acrylic and methacrylic esters of C₁ -C₁₂aliphatic alcohols, hydroxy alkyl esters of acrylic and methacrylicacids, C₁ -C₄ alkyl/C₂ -C₄ amino alkyl esters of acrylic and methacrylicacids, styrene and alkyl substituted styrene monomers, vinyl esters, C₁-C₈ dialkyl maleates, N-vinyl pyrrolidone, and N-substituted alkyl (C₁-C₈) maleamic acid, wherein all percentages total 100% and theimprovement comprises neutralizing at least 70% of the carboxylic acidfunctionalities with an alkaline neutralizing agent comprising at leastone base selected from the group consisting of NaOH or KOH, such thatthe tolerance of the copolymer to hydrocarbons is enhanced.
 2. Anaerosol hairspray formulation comprising 0.50 to 12% (by wt.) of thehair fixing compositio of claim 1, 8-90% (by wt.) of an alcohol solvent,and 10-85% (by wt.) of a nonhalogenated hydrocarbon propellant.
 3. Theformulation of claim 2, wherein the alcohol solvent is a C₁ -C₄ straightor banched chain alcohol.
 4. The formulation of claim 2, wherein thenonhalogenated hydrocarbon propellant is selected from group consistingof C₃ -C₆ straight chain hydrocarbons, C_(4-C) ₆ branched chainhydrocarbons, and mixtures thereof.